<p>The catalytic cracking of high-boiling chlorosilanes, such as Si₂Cl₆—common by-products in polysilicon production—into lower-boiling-point chlorosilanes is essential for their reuse. However, conventional liquid-phase amine catalysts suffer from limited durability and low economic viability due to deactivation caused by metal impurities such as Al³⁺ and Ti⁴⁺. In this work, a novel solid-state guanidine-grafted Merrifield resin (G-M-resin) catalyst&#xa0;was successfully synthesized via nucleophilic substitution. Significantly, the newly developed G-M-resin catalyst exhibits excellent durability, high efficiency<i>,</i> and recyclability in the catalytic cracking of Si₂Cl₆. After five reaction cycles, the G-M-resin catalyst maintains high catalytic efficiency, with only a 9% loss in the presence of Al³⁺ and a 23.6% loss with both Al³⁺ and Ti⁴⁺. In contrast, a conventional organic amine catalyst suffered a 40.8% loss of activity under Al³⁺ and was completely deactivated when both metal ions were present. The superior stability of the G-M-resin catalyst originates from the low binding energy between the grafted guanidine groups and the interfering metal ions (Ti⁴⁺ and Al³⁺), thereby effectively preserving the active sites from deactivation.&#xa0;Furthermore, the solid-state design of the G-M-resin catalyst facilitates its regeneration, allowing for full recovery of initial performance after reactivation. This addresses a key limitation associated with conventional liquid amine catalysts. This work presents a durable and regenerable solid catalyst for converting high-boiling chlorosilanes, offering a promising strategy for maintaining catalytic activity in challenging environments.</p>